Conjugation of bioactive molecules to a fluorescent dithiomaleimide by photoinduced and BEt3-initiated thio-click reactions

Lászlõ Lázár, Miklõs Nagy, A. Borbás, P. Herczegh, M. Zsuga, S. Kéki

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Two versions of the free-radical thiol-ene addition, a photoinduced reaction in the presence of 2,2-dimethoxy-2-phenylacetophenone, and a UV-light-free hydrothiolation using triethylborane as the initiator, were studied for the conjugation of fluorescent dithiomaleimide to biologically active compounds. A dithiomaleimide derivative bearing a vinyl ether functionality was prepared as the alkene partner. This was coupled with a range of thiols, including thiosugars, captopril, N-acetyl-L-cysteine, and sodium 2-sulfonatoethanethiol. The Et3B-initiated method was superior to the photoinduced reaction, as it minimized decomposition of the sensitive maleimide group. The vinyl ether derivative and the addition products showed green light emission in tetrahydrofuran. The compounds all showed almost identical absorption and emission spectra, proving that the structure of the thiols has no influence on the fluorescence properties of the maleimide part of the molecules. The hydrothiolation products showed relatively high quantum yields. Thio-click chemistry and maleimide chemistry were combined, for the first time, to couple fluorescent dithiomaleimide to biologically active compounds. Of the two activation methods tested, Et3B-initiated hydrothiolation was superior to photoinduced variants. All of the hydrothiolation products showed green fluorescence with relatively high quantum yields.

Original languageEnglish
Pages (from-to)7675-7681
Number of pages7
JournalEuropean Journal of Organic Chemistry
Volume2015
Issue number35
DOIs
Publication statusPublished - Dec 1 2015

Fingerprint

activity (biology)
conjugation
Sulfhydryl Compounds
thiols
Quantum yield
Molecules
Thiosugars
ethers
Bearings (structural)
products
Fluorescence
Click Chemistry
chemistry
Derivatives
Methyl Green
molecules
fluorescence
Captopril
cysteine
Light emission

Keywords

  • Carbohydrates
  • Click chemistry
  • Fluorescence
  • Photochemistry
  • Radical reactions
  • Thiols

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry

Cite this

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abstract = "Two versions of the free-radical thiol-ene addition, a photoinduced reaction in the presence of 2,2-dimethoxy-2-phenylacetophenone, and a UV-light-free hydrothiolation using triethylborane as the initiator, were studied for the conjugation of fluorescent dithiomaleimide to biologically active compounds. A dithiomaleimide derivative bearing a vinyl ether functionality was prepared as the alkene partner. This was coupled with a range of thiols, including thiosugars, captopril, N-acetyl-L-cysteine, and sodium 2-sulfonatoethanethiol. The Et3B-initiated method was superior to the photoinduced reaction, as it minimized decomposition of the sensitive maleimide group. The vinyl ether derivative and the addition products showed green light emission in tetrahydrofuran. The compounds all showed almost identical absorption and emission spectra, proving that the structure of the thiols has no influence on the fluorescence properties of the maleimide part of the molecules. The hydrothiolation products showed relatively high quantum yields. Thio-click chemistry and maleimide chemistry were combined, for the first time, to couple fluorescent dithiomaleimide to biologically active compounds. Of the two activation methods tested, Et3B-initiated hydrothiolation was superior to photoinduced variants. All of the hydrothiolation products showed green fluorescence with relatively high quantum yields.",
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T1 - Conjugation of bioactive molecules to a fluorescent dithiomaleimide by photoinduced and BEt3-initiated thio-click reactions

AU - Lázár, Lászlõ

AU - Nagy, Miklõs

AU - Borbás, A.

AU - Herczegh, P.

AU - Zsuga, M.

AU - Kéki, S.

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